EP0041732B1 - Celulle électrolytique avec une membrane échangeuse d'ions améliorée et procédé pour faire fonctionner cette cellule - Google Patents

Celulle électrolytique avec une membrane échangeuse d'ions améliorée et procédé pour faire fonctionner cette cellule Download PDF

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EP0041732B1
EP0041732B1 EP81104462A EP81104462A EP0041732B1 EP 0041732 B1 EP0041732 B1 EP 0041732B1 EP 81104462 A EP81104462 A EP 81104462A EP 81104462 A EP81104462 A EP 81104462A EP 0041732 B1 EP0041732 B1 EP 0041732B1
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Prior art keywords
membrane
ion exchange
cell
pendant
membranes
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German (de)
English (en)
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EP0041732A1 (fr
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Bobby Ray Ezzell
William Paul Carl
William August Mod
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Dow Chemical Co
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • Membranes have been developed for that purpose which are substantially hydraulically-impermeable, but which will permit hydrated Na + ions to be transported from the anolyte portion to the catholyte portions, while substantially preventing transport of CI- ions.
  • Such cells are operated by flowing a brine solution into the anolyte portion and by providing salt-free water to the catholyte portion to serve as the caustic medium.
  • the anodic reactions and cathodic reactions are the same regardless of whether a membrane cell or a diaphragm cell is employed.
  • KWH kilowatt hours
  • the polymers used in the prior art as membranes are generally copolymers formed by copolymerizing a monomer chosen from the group of fluorinated vinyl compounds composed of vinyl fluoride, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and tetrafluoroethylene with an ion exchange functional (or group easily converted to ion exchange functional) vinyl ether monomer.
  • the carboxylic acid monomers are represented by similar structures where the sulfonyl group has been replaced with either a carboxylic acid or a group such as that is easily converted to a carboxylic acid (U.S. Patent 4,065,366, Brit. 1,497,748; 1,497,749; 1,518,387). In one case (U.S.
  • the membrane is composed of a terpolymer made by selecting one monomer from the group of perfluorovinyl compounds listed above and the other two from different carboxylic acid functional monomers.
  • One is chosen from a group represented by where A represents a carboxylic acid or derivative and the other from a group represented by where A' is defined as A above.
  • Two different functional monomers were used in the above case to achieve desirable physical properties of the polymers.
  • U.S. Patents 4,025,405 and 4,192,725 and GB-A-1184321 show electrolytic cells having a stable, hydrated, selectively permeable, electrically conductive membrane.
  • the membrane is a film of fluorinated copolymer having pendant sulfonic acid groups containing recurring structural units of the formula: and where R is in which R' is F or perfluoroalkyl of 1 to 10 carbon atoms; Y is F or CF 3 ; m is 1, 2 or 3; n is 0 or 1; X is F, Cl, H, CF 3 ; X' and X are CF 3 - (CF 2 ) z wherein Z is 0-5; the units of formula (1) being present in an amount of from 3-20 mole percent.
  • An electrolytic cell and a process to use the cell are provided.
  • the electrolytic cell is separated into an anode compartment and a cathode compartment by a fluorinated polymer membrane; wherein the membrane has:
  • Any holes or tears that develop in the film lead to contamination of the caustic product in the catholyte with salt from the anolyte and even worse, can lead to explosive mixtures of hydrogen in chlorine when cathodes are used that produce hydrogen along with attendant production of chlorine on the anode.
  • fluoropolymers in general, meet the chemical requirements of the chlor-alkali cell. These fluoropolymers can be substituted with other halogen atoms such as chlorine or bromine that are not reactive in the cell environment, but, although contrary to some teachings, these polymers should not contain hydrogen atoms on carbons that make up the main polymer backbone. Carbon- hydrogen bonds are chemically attacked by both oxidation from the anolyte components and caustic in the catholyte. Chemical attack on the polymer backbone can lead to reduced molecular weight by carbon-carbon bond cleavage and thus to severe damage to film physical properties.
  • halogen atoms such as chlorine or bromine
  • a highly crystalline fluoropolymer made from simple, unsubstituted monomers such as tetrafluoroethylene is tough, but has extremely high melting or softening temperatures. Fabrication is difficult or near impossible by simple techniques such as melt extrusion. Homopolymers of long chain, terminal fluorocarbon olefins which result in polymers having many pendant groups are difficult to prepare because of having a relatively unreactive olefin site and when formed are often low molecular weight, waxy, amorphous solids having little, if any, plastic quality. Materials of this nature are useless as films. Copolymers of the two type monomers described above often have properties, better than the homopolymers.
  • Copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ethers (US Patent 3,896,179) and halofluoroalkyl vinyl ethers have excellent physical properties and can be conveniently melt fabricated into films.
  • polymers with a limited number of pendant groups can maintain most of the favorable physical characteristics of the parent (no long pendant groups) polymer and also lend itself to simple fabrication.
  • a simple fluorocarbon olefin such as tetrafluoroethylene or chlorotrifluoroethylene
  • a monomer having a halofluoro or perfluoro chain having no ion exchange functionality attached to the olefin function.
  • polymers are selected from the above class of polymers that contain a sufficient (greater than 60 mole percent) amount of the simple, non pendant group originating, monomer such as tetrafluoroethylene, tough, easily fabricated films result that give outstanding performance when used as membranes in chlor-alkali cells. These films may or may not be supported by materials such as polytetrafluoroethylene scrim.
  • the concentration of the sulfonate ion exchange functional group in the polymers is also critical to the performance of the materials as membranes in electrolytic cells. Concentration of the functional group in the dry polymer is expressed herein as equivalent weight, which is defined as the formula weight of the polymer containing one equivalent of the functional group. It can be defined and conveniently determined, by standard acid-base titration, as the weight of the polymer, having the functional group, the sulfonic acid group in the present invention, in the acid form, required to neutralize one equivalent of base.
  • equivalent weight which is defined as the formula weight of the polymer containing one equivalent of the functional group. It can be defined and conveniently determined, by standard acid-base titration, as the weight of the polymer, having the functional group, the sulfonic acid group in the present invention, in the acid form, required to neutralize one equivalent of base.
  • equivalent weight which is defined as the formula weight of the polymer containing one equivalent of the functional group. It can be defined and conveniently determined, by standard acid-base
  • Sulfonic acid membranes having lower equivalent weight allow excessive migration of hydroxide ions from the catholyte to the anolyte portion of the cell and thus result in excessively low current efficiency. It has been found that equivalent weights of at least part of the membranes of the current invention can be substantially less than 1100 and still be useful in chloralkali cells. This is particularly true when the pendant group having the ion exchange functional group is short. In fact, particularly preferred polymers of the present invention are made using the ion exchange functional monomer as opposed to the functional monomer of the prior art. One terpolymer having an equivalent weight of 900 is shown in the examples to perform substantially better than an 1100 equivalent weight copolymer of the prior art. It is thought that equivalent weights as low as 600, when the pendant group having the sulfonic acid functionality is short, should be operable in chlor-alkali cells.
  • the Figure shows the results of using various ion exchange membranes in an electrolytic cell for the electrolysis of a NaCl brine solution. For each membrane tested, the figure shows its operational voltage, its current efficiency and the concentration of the caustic produced in the cell.
  • a series of ion exchange membranes were individually tested in an electrolytic test cell.
  • the cell had an anode and a cathode with the ion exchange membrane being evaluated positioned therebetween, thus separating the cell into an anode chamber and a cathode chamber.
  • Each electrode had a square shape and an area of 8.63 square inches (55,68 cm 2 ).
  • Each electrode had a solid, metal stud welded to it.
  • Each stud passed through a wall of the cell and was provided with leak proof seals. Both studs were connected to a power supply.
  • the stud connected to the anode was constructed of titanium, while the stud connected to the cathode was constructed of steel.
  • the anode, itself, was an expanded titanium mesh screen coated with a RuO z - TiO z mixture, while the cathode was constructed from woven steel wires.
  • the anode chamber was filled with a saturated NaCl brine solution (approximately 25 weight percent NaCI) and catholyte chamber was filled with a caustic solution having approximately 12 weight percent NaOH concentration.
  • the cell was energized by applying a. constant current of approximately 8.63 amps, to give a current density of 1.0 amps per square inch (0,155 amps per cm 2 ) of electrode area.
  • a saturated brine solution (approximately 25 weight percent NaCI) was flowed into the anode chamber at a rate sufficient to maintain the concentration of the anolyte leaving the cell at approximately 17-20 weight percent NaCI.
  • Deionized water was flowed into the catholyte chamber, in a similar manner, at a rate sufficient to maintain the catholyte leaving the cell at a desired NaOH concentration.
  • the NaOH concentration- was varied in order to determine the cell operation over a range of caustic concentrations.
  • the temperature of the cell was controlled throughout each evaluation at about 80°C by means of an immersion heater connected to a thermocouple inserted into the anolyte chamber.
  • the cell voltage was constantly monitored by measuring the difference in voltage potential between the anode stud and the cathode stud.
  • the cell was operated for several days to reach equilibrium. Then current efficiency was determined by collecting the catholyte leaving the cell for a given period of time, usually 16 hours, and determining the amount of NaOH actually produced, as compared to the amount theoretically produced at the applied current.
  • This membrane was received from E. I. DuPont in the acid form and was treated in the TEA solution as received.
  • the figure shows the results obtained from the evaluation of various membranes in the above described cell, except for membranes designated as F and G.
  • the data shown for these latter two membranes was obtained from published literature and is inserted for comparative purposes.
  • the figure shows the relationship of the current efficiency of the cell to the caustic concentration of the catholyte as it leaves the cell.
  • the numbers in parenthesis beside each curve represent average cell operating voltages over the range of caustic concentrations under which each membrane was tested.
  • Membranes designated as B and C are copolymers differing only in the relative amounts of TFE and the functional monomer. Thus, membrane C has more ion exchange functionality than membrane B, which is reflected in their 860 and 1375 eq. wts. respectively.
  • Membranes designated as D, E and H are all membranes which have pendant sulfonyl ion exchange groups and have pendant, substantially fluorinated carbon groups which have no ion exchange functionality. As shown by their respective equivalent weights of 1240, 900 and 1350, they have differing amounts of ion exchange functionality.
  • a direct comparison of cells having membrane B with cells having membrane E shows that where the two types of membranes operate at essentially equal current efficiencies, the cell containing the membrane having pendant, substantially fluorinated carbon groups which have no ion exchange functionality, as well as containing pendant sulfonyl ion exchange groups, operates at substantially (14%) lower voltage than the cell having a membrane which does not have a pendant, substantially fluorinated carbon group which has no ion exchange functionality, but has only the sulfonyl containing pendant group.
  • a comparison of the cell containing membrane C with a cell containing membrane E demonstrates that while the cells operate at approximately the same voltage, the cell having a membrane which has pendant substantially fluorinated carbon groups not having ion exchange functionality, as well as containing pendant sulfonyl containing groups, operates at a substantially higher current efficiency than the cell containing the membrane which has only pendant sulfonyl containing groups.
  • the table shows a comparison of polymers A, B, C, D, E and H where power consumption per metric ton of caustic has been calculated with all cells operating at 12% caustic.
  • the table clearly demonstrates the superiority of the cells which have membranes (D, E and H) having two pendant groups; one pendant group having sulfonyl ion exchange groups and one pendant, substantially fluorinated carbon group which has no ion exchange groups, as compared to cells which have membranes (B and C) having only one pendant group, a sulfonyl containing group.
  • This comparison between the cells containing membranes D, E and H as opposed to cells containing membranes B and C is made where the membrane thicknesses are similar.
  • the table shows that even when the thickness of membrane A (the prior art membrane having only sulfonyl containing pendant groups) is only one-fourth (1/4) that of membranes D, E and H (which have two types of pendant groups) the latter perform equally (D) or better (E).

Claims (13)

1. Membrane de polymère fluoré pour utilisation dans une cellule électrolytique comprenant:
(a) un copolymère de CFXCF2 et ayant au moins 60 moles pour cent de CFXCF2, où X = F ou CI;
(b) un poids équivalent d'échange d'ions d'au moins 600 et .
(c) des groupes échangeurs d'ions sulfonyle pendants; caractérisée par le fait qu'elle comprend:
(d) des groupes pendants supplémentaires de carbone substantiellement fluoré qui n'ont pas de fonctionnalité d'échange d'ions.
2. Membrane selon la revendication 1, dans laquelle le groupe pendant échangeur d'ions sulfonylé est représenté par la formule générale:
Figure imgb0020
où
n = 0 ou un nombre entier plus grand que zéro;
X = F, CI ou Br;
M = de l'hydrogène ou un métal alcalin;
Rf et Rf sont choisis indépendamment dans le groupe constitué par F, CI, un fluoroalcoyl et un chlorofluoroalcoyl;
a = zéro ou un nombre entier plus grand que zéro;
b = zéro ou un nombre entier plus grand que zéro, avec la condition que a + b # 0.
3. Membrane selon l'une des revendications 1 ou 2, dans laquelle les groupes pendants de carbone fluoré n'ayant pas de fonctionnalité d'échange d'ions sont représentés par la formule générale:
Figure imgb0021
où
X' et X"' sont choisis indépendamment dans le groupe constitué par F, CI et Br
n', a et b' sont, indépendamment, zéro ou un nombre entier plus grand que zéro
Rf et R'f sont choisis, indépendamment, dans le groupe constitué par le fluor, le chlore, des fluoroalcoyles et des chlorofluoroalcoyles.
4. Membrane selon les revendications 1, 2 ou 3, où la membrane a un poids équivalent d'échange d'ions compris entre 600 et 2000.
5. Membranes selon les revendications 1, 2 ou 3, où la membrane a un poids équivalent d'échange d'ions compris entre 800 et 1600.
6. Membrane selon la revendication 3, dans laquelle a et a' = 0-3; b et b' = 0-3; Rf = CI ou F et R'f= Cl ou F.
7. Membrane selon la revendication 6, dans laquelle n et n' = 0-3 et X et X' = CI ou F quand n ≠ 0.
8. Membrane selon la revendication 1, 2 ou 3, dans laquelle n = 0; n' = 0 ou 1 et X' = F ou CI quand n' = 1.
9. Membrane selon la revendication 1, 2 ou 3, dans laquelle n = 1; X = F ou CI; n' = 0 ou 1 et X' = F ou CI quand n' = 1.
10. Membrane selon la revendication 1, 2 ou 3, dans laquelle n = 0; n' = 0 et X"' = CI.
11. Membrane selon la revendication 1, 2 ou 3, dans laquelle n = 0; n' = 1; X' = CI et X"' = CI.
12. Utilisation d'une membrane selon l'une des revendications 1 à 11 dans une cellule d'électrolyse d'halogénure de métal alcalin comme moyen pour la séparation d'une chambre contenant une anode et d'une chambre contenant une cathode.
13. Cellule électrolytique ayant une anode dans une chambre d'anode, une cathode dans une chambre de cathode et une membrane échangeuse d'ions séparant la chambre d'anode de la chambre de cathode, caractérisée par le fait que la membrane échangeuse d'ions est une membrane de polymère fluoré selon l'une des revendications 1 à 11.
EP81104462A 1980-06-11 1981-06-10 Celulle électrolytique avec une membrane échangeuse d'ions améliorée et procédé pour faire fonctionner cette cellule Expired EP0041732B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81104462T ATE9721T1 (de) 1980-06-11 1981-06-10 Elektrolytische zelle mit verbesserter ionenaustauschermembran und verfahren zum betrieb dieser zelle.

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Application Number Priority Date Filing Date Title
US158429 1980-06-11
US06/158,429 US4470889A (en) 1980-06-11 1980-06-11 Electrolytic cell having an improved ion exchange membrane and process for operating

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EP0041732A1 EP0041732A1 (fr) 1981-12-16
EP0041732B1 true EP0041732B1 (fr) 1984-10-03

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US (1) US4470889A (fr)
EP (1) EP0041732B1 (fr)
JP (1) JPS5779184A (fr)
KR (1) KR850000101B1 (fr)
AT (1) ATE9721T1 (fr)
AU (1) AU547061B2 (fr)
BR (1) BR8103718A (fr)
CA (1) CA1185921A (fr)
DE (1) DE3166440D1 (fr)
ZA (1) ZA813902B (fr)

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Also Published As

Publication number Publication date
DE3166440D1 (en) 1984-11-08
JPS5779184A (en) 1982-05-18
JPS6123933B2 (fr) 1986-06-09
AU547061B2 (en) 1985-10-03
AU7160581A (en) 1981-12-17
ZA813902B (en) 1983-01-26
EP0041732A1 (fr) 1981-12-16
BR8103718A (pt) 1982-03-02
US4470889A (en) 1984-09-11
KR850000101B1 (ko) 1985-02-22
ATE9721T1 (de) 1984-10-15
KR830006473A (ko) 1983-09-24
CA1185921A (fr) 1985-04-23

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